The problem is that the vault file can be copied, which means this is now "something you and your attacker have". Even worse, it's not just the (probably encrypted) vault file: if your computer ever gets compromised, it is trivial to wait until you unlock the vault, at which point they can extract the now-plaintext TOTP secrets.
The way I understand it, the "something you have" factor is something which is intrinsically only a single item: either you have it, or you do not. If it can be copied, one of the copies could be compromised without you noticing - and because it's a copy you wouldn't even be able to revoke it without changing your own token too.
If that happens, nothing will save you. The malware can just grab your session tokens whenever you log in, then do whatever it pleases.
I don't know anyone who buy a second smartphoe to make it sure 2FA is on a separate device.